Omicron-(cyano-pyridyl) o, o&#39; di-lower-alkyl phosphate and phosphoro thioate esters and derivatives thereof



U itsd State Paten 3,399,205 0 (CYANO PYRIDYL)0,0' DI LOWER AL- KYLPHOSPHATE AND PHOSPHORO THIOATE ESTERS AND DERIVATIVES THEREOFRaymond'H. Rigterink, MidIa'n'd,"lVIich., assignor to The Dow ChemicalCompany, Midland,Mich.', a corporation of Delaware Y Y 1 No Drawing.Continuation-impart of application Ser. No. 375,369, June15, 1964. Thisapplication Sept. 21, 1967,

Ser. No. 669,395 p 9 Claims. (Cl. 260294.8)

ABSTRACT OF THE'DI SCLOSURE Cyanopyridyl phosphorus compounds having theformula.

NEG

in which Z represents oxygen or sulfur; X represents bromo or chloro; Rrepresents loweralkoxy; R represents loweralkoxy, amino, orloweralkylamino; and n represents an integer of from 0 to 3, bothinclusive, are claimed. The compounds are useful as parasiticides. ,Thepresent invention is directed to cyanopyridyl phosphorus compoundshaving the formula This application is a continuation-in-part of US.patent application Ser. No- 375,369, filed June 15, .1964, nowabandoned.

These compounds are crystalline solid or viscous materials which aresomewhat soluble in many common organic solvents and of very lowsolubility in water. The compounds are useful as parasiticides and areespecially adapted to be employed as active toxicants in compositionsfor the control, and, in particular, for the selective control, of anumber of arachnid, insect, helminth, bacterial and fungal organisms andaquatic animals; such as cockroaches, beetles, mites, ticks, worms,Southern armyworms, aphids, flies, mosquites, cattle grubs, screw worms,trash fish, snails, ascarids, nematodes, roundworms and plum curculio.

The novel compounds of the present invention are prepared by any one ofseveral methods. In a preferred method, the compounds are prepared byreacting a phosphorochloridate or phosphorochloridothioate having theformula K Patented Aug. 1

with an alkalimetal salt or a teriaryamine: salt of a cyanopyridinol,having the .formula p I j o-alkalimetal respectively. H 1

.The reactionconveniently, is carried out in an inert organic liquidsuch as acetone, dimethylf ormamide, car bon tetrachloride, chloroform,benzene, toluene, isobutyl methyl ketone, or methylene dichloride. Theamounts of the reactants to be employed are not critical, some of thedesired product being obtained when employing the reactants in anyamounts. In the preferred method of op eration, good results areobtained when employing substantially equimolecular proportions of thecyanopyridinol salt and phosphorochloridate or phosphorochloridothioate.The reaction takes place smoothly at a reaction temperature of from 0 to100 C., with the production of the desired product and a chloridebyproduct which appears as an alkali metal chloride or as a tertiaryamine hydrochloride salt. In carrying out the reaction, the reactantsare mixed and contacted together in any convenient fashion, and theresulting mixture maintained for a period of time in the reactiontemperature range to complete the reaction. Following the completion ofthe reaction, the reaction mixture is washed with water and any organicreaction medium removed by fractional distillation under reducedpressure to obtain the desired product as a residue. This product can befurther purified by conventional procedures such as washing with waterand dilute aqueous alkali metal hydroxide, solvent extraction andrecrystallization.

In an alternative procedure, those compounds of the present invention inwhich R represents amino or loweralkylamino can be prepared by reactinga phosphorodichloridate or phosphorodichloridothioate having the formulawith an alkali metal salt or tertiaryamine salt of a cyanopyridinol, aspreviously defined, to form an intermediate cyanopyridylphosphorochloridate or phosphorochloridothioate having the structure llO-P-R All This intermediate is thereafter reacted with an amino compoundsuch as ammonia or a loweralkylamine to produce the desired productwherein R represents amino or lower-alkylamino. The reaction ofphosphorodichloridate same reaction'mediu m. Good results are obtainedwhen employing'substantially equimolecular proportions of thephosphorodichloridate or phosphorodichloridothioate and cyanopyridinolsalt and at least two molecular proportions of amino compound. Thereaction with the cyanopyridinol salt is somewhat exothermic and iscarried out at temperatures of from -50 to 25 C. The reaction betweenthe intermediate cyanopyridyl phosphorochloridate orphosphorochloridothioate and the amino compound is also exothermic andtakes place at the temperature range of from to 60 C. The temperaturescan be controlled by regulating the rate of mixing and contacting thereactants together and by external cooling. The byproduct in both stepsof the reaction is chloride. In the first step, the chloride appears asalkali metal chloride or tertiaryamine hydrochloride. In the secondstep, the chloride appears and is removed as the hydrochloride salt ofthe amine or ammonia reactant. The desired product can be separated inaccordance with the conventional proce'dures as previously described.

In an alternative procedure, the compounds of the present invention canbe prepared by reacting phosphorus oxychloride or phosphorusthiochloride with a cyanopyridinol salt as previously defined to form anintermediate cyanopyridyl phosphorodichloridate orphosphorodichloridothioate. Good results are obtained when employingsubstantially equimolecular proportions of the reactants. The reactiontakes place readily at temperatures of from 50 to 80 C. with theproduction of the desired product and halide of reaction. Theintermediate is thereafter reacted with one or two alkali metalloweralkanolate reactants of the formula alkali metal--R or, when R inthe desired product represents amino or loweralkylamino, with one alkalimetal loweralkanolate reactant and with an amino compound such asammonia or a loweralkylamine, to produce the desired compound either asa diester or triester product. The reaction takes place at temperaturesat which chloride of reaction is formed. This chloride appears in thereaction mixture as alkali metal chloride, or, when an amino compound isemployed as reactant, as the hydrochloride salt of the amino compound.Good results are obtained when operating at temperatures of from 10 to60 C. and employing substantially stoichiometric amounts of thereactants. Upon completion of the reaction, the desired product isseparated by conventional procedures as previously described.

The reaction, of 'whatever sort, by which a cyanopyridyloxy moiety isintroduced into a compound of the present invention, occurs at thecyanopyrid'mol hydroxy site, or at the oxymetal or hydroxylamine site ofthe derivative thereof, and other portions of the canopyridyloxy moietyremain essentially unchanged. Thus the isomery of the cyanopyridyloxyportion of the present compounds can be controlled by choice of theisomery of the starting cyanopyridyl compound.

The desirable properties of the present products are inherent in thepure compounds; and when highly selective properties are to be reliedupon the purified com- 1 pounds will be preferred. However, for manyappications, wherein low cost is a major consideration, the reactionmixture wherein the product was prepared can be used With no stepswhatsoever of separating or purifying prod- A preferred sub-groupof thesubject compounds are these compounds of the formula Example1.O-(5-cyano- 2 pyridyl) 0,0-diethyl phosphorothioate5-cyano-2-pyridinol (7.0 grams; 0.058 mole), anhydrous sodium carbonate(6.5 grams; 0.058 mole), and 100 milliliters of dimethylformamide arestirred together at room temperature to produce a liquid mediumcontaining the sodium salt of the 5-cyano-2-pyridinol. 0,0- diethylphosphorochloridothioate (10.5 grams; 0.058 mole) is added in oneportion thereto with stirring. Thereafter, the resulting reaction mixturis heated to a temperature of about 60 C. and maintained at atemperature of 60-65 C. for 1 hour with stirring to complete thereaction. The reaction mixture is then filtered and the reaction mediumremoved from the filtrate by distillation under reduced pressure toobtain the O-(5- cyano-Z-pyridyl) 0,0-diethyl phosphorothioate productas 'a residue. The product residue is dispersed in a liquid consistingof 100 milliliters of benzene and 50 milliliters of water, the resultingdispersion filtered, and the henzene portion thereof separated andwashed twice with 50 milliliter portions of water. Water is removed fromthe washed portion over a dehydrating agent, the dried said portionfiltered, and the solvent removed from the filtrate by evaporation undersubatmospheric pressure to separate the product. The product is purifiedby mixing it with a quantity of petroleum ether boiling at 60-70 C. themixture heated to boiling and thereafter cooled, traces of water removedfrom the cooled mixture over a dehydrating agent, the dried mixturefiltered, and the petroleum ether removed by evaporation undersubatmospheric pressure. The purified product is a liquid materialhaving a refractive index 11 1.5238.

Example 2.--O-( 2-cyano-3-pyridyl) 0,0-diethyl phosphorothioate Inprocedures essentially identical with those employed in Example 1,O-(2-cyano-3-pyridyl) 0,0-diethyl phosphorothioate is prepared. Theproduct has a molecular weight of 272.3, is a liquid materiah'and has arefractive index n;; 1.5160.

Example 3. O-(6-cyano-3-pyridyl) O-isobutyl ethylphosphoramidate6-cyano-3-pyridinol (6.0 grams; 0.05 mole) and sodium carbonate (5.3grams; 0.05 mole) are mixed together in 200 milliliters of isobutylmethyl ketone as solvent. Thereafter, the mixture is cooled to about 40C.

uct compounds therefrom, since byproducts of reaction are oftenunobjectionable. Likewise, incompletely purified products can be used,when desired.

A preferred embodiment according to the present invention constitutesthose subject compounds wherein the cyanopyridyl moiety is a radical ofthe following formula:

and O-isobutyl phosphorodichloridate (9.6 grams; 0.05 mole) added all atonce with stirring. Stirring is continued for one hour allowing thetemperature to rise to 25 C. As a result of these operations, there isprepared a liquid mixture containing the intermediate O-isobutylO-(6-cyano-3-pyridyl) phosphorochloridate; this liquid mixture is cooledto a temperature of about 0 C. Ethylamine (4.5 grams; 0.1 mole) is thenadded portionwise with stirring and cooling to the said mixture; theaddition is carried out in 10 minutes and at a temperature of from 0 to10 C. Stirring is then continued for one hour and the temperatureallowed to rise to 25 C. in order that the'reaction be completed. Thereaction mixture is thereafter washed with water and the reaction mediumremoved by fractional distillation under reduced pressure to obtain theO-isobutyl O-(6-cyano-3-pyridyl) ethylphosphoramidate product having amolecular weight of 283.

In similar manners, other compounds representative of the presentinvention are prepared as follows:

From O-n-butyl diethylphosphormidochloridate and the sodium salt of3-cyano-2-pyridinol, O-(3-cyano-2- pyridyl) O-n-butyldiethylphosphoramidate product having a molecular weight of 309.3.

From O-isopropyl methylphosphoramidochloridate an the sodium salt of5-cyano-3-bromo-2-pyridinol, O-(5- cyano-3-bromo-2-pyridyl) O-isopropylmethylphosphoramidate product having a molecular weight of 334.1. Thesodium salt of 5-cyano-3-bromo-2-pyridinol is prepared by reacting5-cyano-3-bromo-2-pyridinol, a compound melting at 252-257 C., withsodium hydroxide.

From O-methyl di-n-butylphosphoramidochloridothioate and the sodiumsaltof 4-cyano-2-pyridino1, O-(4- cyano-2-pyridyl) O-methyldi-n-butylphosp'horamidothioate product having a molecular weight of341.4.

From 0,0-diethyl phosphorochloridothioate and the sodium salt of5-cyano-3,6-dibromo-2-pyridinol, -(5- cyano-3,6-dibromo-2-pyridyl)0,0-diethyl phosphorothioate product having a molecular weight of 429.2.

' From 0,0-dimethyl phosphorochloridate and the sodium salt of-cyano-2-pyridinol, O-(5-cyano-2- pyridyl) 0,0-dimethyl phosphateproduct having a molecular weight of 228.2.

From '0,0-diethyl phosphorochloridothioate and the sodium salt of5-cyano-3-chloro-2pyridinol, O-(S-cyano- 3-chlo'ro-2-pyridyl)0,0-diethyl phosphorothioate product. The product is a viscous liquidhaving a refractive index n of 1.5310. The sodium salt of5-cyano-3-chloro- Z-pyridinol is prepared by reacting5-cyano-3-chlor0-2- py ridinol, a compound melting at 241-245 C., withsodium carbonate.

From O-n-propyl isobutylphosphoramidochloridothiate and the sodium saltof 6-cyano-2-pyridinol, 0-(6- cyano-2-pyridyl) O-n-propylisobutylphosphoramidothioate product having a molecular weight of 301.4.

From 0,0-diethyl phosphorochloridothioate and the sodium salt of6-cyano-3,5-dichloro-2-pyridinol, 0-(6- cyano-3,5-dichloro-2-pyridyl)0,0-diethyl phosphorothioate product having a molecular weight of 341.2.

From O-n-butyl O-methyl phosphorochloridothioate and the sodium salt of'3-cyano-5-chloro-4-pyridinol, 0- (3 cyano-5-chloro-4-pyridyl)O'-n-butyl O-methyl phosphorothioate product having a molecular weightof 320.7.

From 0,0-diethy1 phosphorochloridate and the sodium saltof5-cyano-2-pyridinol, O-(5-cyano-2-pyridyl) 0,0- diethyl phosphateproduct having 'a molecular weight of 256.2 and a refractive index of n1.4862.

From O-isopropyl methylphosphoramidochloridothioate and the sodium saltof 5-cyano-2-pyridinol, 0 (5- cyano-Z-pyridyl) O-isopropylmethylphosphoramidothioate product having a molecular weight of 271.3.

From 0,0-di-sec-butyl phosphorochloridate and the sodium salt of3-cyano-5-bromo-2-pyridinol, O(3-cyano- 5-brorno-2-pyridyl)O,O-di-sec-butyl phosphate product having a molecular weight of 391.2.

From 0,0-di-n-propyl phosphorochloridothiate and the sodium salt of5-cyano-2-pyridinol, O-(5-cyano-2- pyridyl) -0,0-di-n-propylphosphorothioate product having a molecular weight of 300.3.

From O-ethyl phosphorodichloridate, the sodium salt of2-cyano-3-pyridinol, and ammonia, O-(2-cyano-3- pyri-dyl) O-ethylphosphoram-idate product having a molecular weight of 227.2.

From 0,0-dimethyl phosphorochloridothioate and the sodium salt of5-cyano-2-pyridinol, O-(5-cyano-2- pyridyl) 0,0-dimethylphosphorothioate product having a molecular weight of 244.2 and meltingat 8586 C. In

a representative preparation, the product was found to have an actualnitrogen content of 11.55 percent ascompared to a theoretical nitrogencontent of 11.45 percent. From 0,0-di-sec-butyl phosphorochloridate andthe sodium salt of 4-cyano-3-pyridinol, O-(4-cyano-3-pyridyl)0,0-di-sec-butyl phosphate product having a molecular weight of 312.3. t

From 0,0-dimethyl phosphorochloridothioate and the sodium salt of5-cyano-3-pyridinol, .O-(5-cyano-3-pyridyl) O,O-dimethylphosphorothioate product having a molecular weight of 234.2 FromO-n-propyl sec-butyl-phosphoramidochloridothioate and the sodium salt of5-cyano-3-chloro-2-pyridinol, 0-(5-cyano-3-chloro-2-pyridyl) O-n-propylsecbutylphosphoramidothioate product having a molecular weight of 347.8.

From O-n-propyl dimethylphosphoramidochloridothioate and the sodium saltof 2-cya-no-4-pyridinol, O- (2-cyano-4-pyridyl) 'O-n-propyldimethylphosphoramidothioate product having a molecular weight of 285.3.

From O-methyl phosphoramidochloridate and the sodium salt of2-cyano-6-bromo-3-pyridinol, O-(2-cyano-6- bromo-3-pyridyl) O-methylp-hosphoramidate product having a molecular weight of 292.

From 0,0-dimethyl phosphorochloridate and the sodium salt of3-cyano-4-pyridinol, O-(3-cyano-4-pyridyl) 0,0-dimethyl phosphateproduct having a molecular weight of 228.2.

From O-methyl methylphosphoram'idochloridothioate and the tertiary-aminesalt of 5-cyano-2-pyridinol, O-(S- cyano-2-pyridyl) O-methylmethylphosphoramidothioate product melting at 697l C.

From 0,0-diethyl phosphorochloridothioate and the sodium salt of3-cyano-4-pyridinol, O-(3-cyano-4-pyridyl) 0,0-diethyl phosphorothioateproduct having a molecular weight of 272.3.

From 0,0diethyl phosphorochloridothioate and the sodium salt of5-cyan0-3,6-dichloro-2-pyridinol, O-(S- cyano-3,6-dichloro-2-pyridyl)0,0-diethyl phosphoro-thioate product having a molecular weight of341.2.

From O-ethyl O-methyl phosphorochloridate and the sodium salt of2-cyano-4-pyridinol, O-(2-cyano-4-pyridyl) O-ethyl O-methyl phosphateproduct having a molecular weight of 242.2.

From 0,0-dimethyl phosphorochloridate and the sodium salt of5-cyano-3,4,6-trichloro-2-pyridinol, O-(5-cyano-3,4,6-trichloro-2-pyridyl) 0,0-dimethyl phosphate product having amolecular weight of 331.5.

From O-isobutyl phosphoramidochloridate and the sodium salt of2-cyano-4-pyridinol, O-(2-cyano-4-pyridyl) O-isobutyl phosphorarnidateproduct having a molecular weight of 255.2.

From 0,0-dimethyl phosphorochloridothioate and the sodium salt of5-cyano-2,4,6-tribromo-3-pyridinol, O-(5-cyano-2,4,6-tribromo-3-pyridyl) O, O-dimethyl phosphorothioate producthaving a molecular weight of 480.9

The compounds of the present invention are useful as parasiticides andparasite repellants in a variety of household, industrial, andagricultural operations. In particular, the compounds are useful for thekill and control of arthropod pest organisms, such as crustaceans,including sow bugs fiddler crabs; arachnids, including spiders, mites,and ticks; myriapods, including centipedes; and insects.

In particular, the compounds of the present invention can be employed togive a quick inactivation of arthropod organisms; this is spoken of as aquick knockdown. Also, the subject compounds exhibit residual activityover long periods of time following utilization in areas the characterof which is determined largely by the presence of inert objects, such.as wood or wood products, fabrics, metal or metallic materials, plasticmaterials, and the like. Because of this excellent residual activity andbecause of the quick knockdown, the subject compounds are particularlysuitable for the control, inside houses, barns, warehouses, publicbuildings, and the like, of arthropod pests, including cockroaches, suchas the German cockroach, American cockroach, and brown-banded cockroach;beetles, such as the black-carpet beetle, confused flour beetle,sawtooth grain beetle, and larder beetle; spiders, silverfish; bedbugs;fleas, such as those on bedding used by household pets, and fiea larvae;mosquitos; box-elder bugs; spiders; mites; ants, centipedes; and flies,such as the common housefly. The subject compounds exhibit negligiblemammalian toxicity at rates which are highly effective for such indoorcontrol of arthropod pests and thus are particularly adapted for suchemployment.

The new cyanopyridyl phosphorus compounds are also very effective forthe control of the many arthropod organisms found on the root or aerialportions of growing plants, including aphids, mites, plant pathogens,and chewing and sucking insects, such as Southern army worm (Prodeniaeridalria), California red scale (Aonidiellzz auranzii), Mexican beanbeetle (Epilachna varivestis), two-spotted spider mite (Tetfalzychusbimaczllatus), and bean aphid (Aplzis abae).

In contrast with the excellent residual activity of the subjectcompounds 'in contact with essentially inert objects, the subjectcompounds, when applied to plants, plant parts, and their habitats toprotect the plants from the attack of arthropod organisms, exhibitresidual control of the organisms over only a relatively brief period oftime. Thus, plants treated with one or more of the present cyanopyridylphosphorus compounds are found shortly thereafter to be free from thecompounds and from substances identifiable as residues of the compounds.

The new compounds can also be included in inks, adhesives, soaps,polymeric materials, cutting oils or in oil or latex paints. Also, thepresent compounds can be distributed in textiles, cellulosic materials,or in grains, or can be employed in the impregnation of wood and lumber.Additionally, they can be applied to seeds. In yet other procedures, thecyanopyridyl phosphorus compounds can be vaporized or sprayed ordistributed as aerosols into the air, or onto surfaces in contact withthe air. In such applications, the compounds manifest the usefulproperties herinbefore described.

The methods of the present invention comprise contacting an arthropodwith an inactivating amount of one of the present cyanopyridylphosphorus compounds. Contacting can be effected by application of thecompound to habitat of arthropods. Representative habitats include soil,air, water, food, vegetation, inert objects, stored matter such asgrains, other animal organisms, and the like. The inactivtaion can belethal, immediately, or with delay, or can be a sub-lethal one in whichthe inactivated arthropod is not able to carry out one or more of itsnormal life processes. This latter situation prevails when one of thesystems of the arthropod, typically the nervous system, is seriouslydisturbed. A preferred embodiment of the present invention comprises theemployrnent of the present method for the kill and control of insectsand arachnids; such employment gives excellent results, particularly incontrol of insects and arachnids that have developed resistance againstother pest-control substances.

The inactivation of an arthropod by the application of an inactivatingamount of one of the cyanopyridyl phosphorus compounds is critical tothe method of the present invention. The cyanopyridyl phosphoruscompound can sometimes be employed in unmodoified form. Frequently,however, the desirable properties of such compound can be utilized onlywhen the compound is modified by the employment with it of a pesticidaladjuvant. Thus, for example, the present compounds are of very lowsolubility in water but are relatively soluble in oils, including plantessential oils. Accordingly, the application of the pure compound, evenby the use of highly sophisticated techniques, to the surface of aplant, commonly results in its dispersion and loss in surface waxes oressential oils; or, in the common situation of early morning applicationwhen the plant is wet with dew, may result inrun-off which leaves theplant with little or no applied product. Also, in aquatic settings, thedesirable properties of the compounds can usually be utilized only whenthe compounds are modified by the employment of a pesticidal adjuvant.Moreover, the pure compound is quickly attacked in outdoor situations bysunlight and air, whereas, incorporated in a pesticidal adjuvant thecompound often derives protection from such influences. Therefore, thepractical employment of the beneficial utilities of the presentcompounds often requires that the compound be composited with one ormore pesticidal adjuvant substances, and the resulting compositions arecomprehended with the present invention.

The composition can be a liquid or a dust; and the adjuvant employed canbe any one or a plurality of materials including aromatic solvents,petroleum distillates, water, or other liquid carriers, propellantsubstances, surface-active dispersing agents, light absorbers, andfinely divided carrier solids. In such compositions, the adjuvantcooperates with the cyanopyridyl phosphorus compound so as to obtain acomposition to facilitate the method of the present invention, and toobtain an improved result. The use of either a surface-active dispersingagent or a finely divided carrier solid and the use of both asurface-active dispersing agent and a finely divided carrier solid,simultaneously, constitute preferred embodiments of the method of thepresent invention. Another preferred embodiment of the present inventionis a composition comprising one or more of the cyanopyridyl phosphoruscompounds, an organic liquid as a solvent and carrier therefor, and apropellant material. Numerous other embodiments will become available tothose skilled in the art in view of the teachings set forth hereinbelow.

The exact concentration of one or more cyanopyridyl phosphorus compoundsin a composition thereof with one or a plurality of adjuvants can vary;it is necessary only that one or more cyanopyridyl phosphorus compoundsbe present in such amount as to make possible the application of aninactivating dosage. In many situations, a composition comprising.0000001 percent of one, or a total of more than one, of thecyanopyridyl phosphorus compounds is effective for the administration ofan inactivating amount thereof to arthropod pest organisms. In otherprocedures, compositions comprising a lesser amount, such as .00000005percent of one, or more than one, of the cyanopyridyl phosphoruscompounds, or a greater amount, such as 0.05 percent of one, or morethan one, of the cyanopyridyl phosphorus compounds, are effective forthe inactivation of arthropod organisms, In still other operations,compositions containing from 0.5 to 98 percent by weight of onecynaopyridyl phosphorus compound, or from 0.5 to 98 percent of a totalof more than one cyanopyridyl phosphorus compound, are convenientlyemployed. Such compositions are adapted to be employed as treatingcompositions and applied to parasites and to their habitats, or to beemployed as concentrates, and subsequently diluted with aditionaladjuvant to produce ultimate treating compositions.

When combining the present toxicants with adhesives, detergents, cuttingoils, paints, polymeric materials, textiles, paper, and other similarproducts, good results are obtained when the compounds are incorporatedin such products in the amount of 0.005 to 0.1 percent by weight, andwhen heavier applications are needed in the amount of from 0.1 to 2.0percent by weight. When one or more than one of the present toxicants iscombined with'wood, excellent results are obtained when the toxicantcompound or compounds are incorporated by conventional treatment of thewood in the amount of from 0.00005 to 0.5 pounds per cubic foot of wood,depending on depth of penetration, exposure, and the like.

In the preparation of dust compositions, the cyanopyridyl phosphorusproduct can be compounded with any of the finely divided carrier solidssuch as pyrophyllite, diatomaceous earth, gypsum and the like; In suchoperations, the finely divided carrier is ground or mixed with one ormore of the cyanopyridyl phosphorus compounds, as active agent, orwetted with a solution of the active agent in avolatile organic solvent.Similarly, dust compositions containing the cyanopyridyl phosphorusproduct can be similarly compounded from various of the solid dispersingagents, such as fullers earth, attapulgite and other clays. These dustcompositions can be employed as treating compositions or can be employedas concentrates and subsequently diluted with additional soliddispersing agent or with pyrophyllite, diatomaceous earth, gypsum andthe like to obtain the desired amount of active agent in a treatingcomposition. Also, such dust compositions can be dispersed in water,with or without the aid of surfactant, to form spray mixtures.

Further, one of the cyanopyridyl phosphorus compounds or a dustconcentrate composition containing such compound can be incorporated inintimate mixture with surface active dispersing agents such as ionic andnonionic emulsifying agents to form spray concentrates. Suchconcentrates are readily dispersible in liquid carriers to form sprayscontaining the toxicant in any desired amount. The choice of dispersingagent and amount thereof employed are determined by the ability of theagent to facilitate the dispersion of the concentrate in the liquidcarrier to produce the desired spray composition.

In the preparation of liquid compositions, the cyanopyridyl phosphorusproduct can be compounded with a suitable water-immiscible organicliquid and surface active dispersing agent to produce an emulsifiableliquid concentrate which can be further diluted 'with water and oil toform spray mixtures in the form of oil-in-water emulsions. In suchcompositions, the carrier comprises an aqueous emulsion, that is, amixture of water-immiscible solvent, emulsifying agent and water.Preferred dispersing agents to be employed in these compositions areoil-soluble and include the non-ionic emulsifiers such as thepolyoxyethylene derivatives of sorbitan esters, complex ether alcoholsand the like. However, oil-soluble ionic emulsifying agents such asmahogany soaps can also be used. Suitable organic liquids to be employedin the compositions include petroleum oils and distillates, toluene,liquid halohydrocarbons and synthetic organic oils.

When operating in accordance With the present invention, thecyanopyridyl phosphorus product or a composition containing the productis applied to the pests to be controlled directly, or by means ofapplication to a portion or portions of their habitat in any convenientmanner, for example, by means of hand dusters or sprayers or by simplemixing with the food to be ingested by the organisms. Application to thefoliage of plants is conveniently carried out with power dusters, boomsprayers and fog sprayers. In such foliar applications, the employedcompositions should not contain any appreciable amounts of anyphytotoxic diluents. In large scale operations, dusts, or low-volumesprays can be applied from an airplane. The present invention alsocomprehends the employment of compositions comprising one of thecyanopyridyl phosphorus compounds, an adjuvant, and one or more otherbiologically active materials, such as insecticides, fungicides,miticides, bactericides, nematocides, and the like, or one or moresynergistic materials.

A preferred and especially convenient matter for the application of oneor more of the present products comprises the use of a self-pressurizedpack formulation which can be used, for example, as a space or surfacespray. Such a formulation can comprise one or more of the cyanopyridylphosphorus compounds, an organic liquid as a solvent andvehicletherefor, and a propellant material which can be a condensed andcompressed gas or a substance which, at room temperature, is a gas underatmospheric pressure butwhichliquefies under superatmospheric pressure.Where the propellant.rnaterial is of the latter type, theself-pressurized pack-formulation is often spoken of as an aerosol.Representative propellants include propane, butane, nitrogren, and thefluorinated hydrocarbons, such as dichlorodifluoromethane andt'richlorofluoromethane. Generally, the propellant constitutes from 25to 95 percent'by weight of the total self-pressurized pack. As vehicle,there can be employed any liquid in which the desired amount of productis capable of being dispersed; preferred vehicles include petroleumdistillates, kerosene, and methylene chloride. The self-pressurized packformulation can also include other materials, such as other biologicallyactive agents or synergists. For further discussion of the use ofself-pressurized pack formulations, see US. Patents 1,892,750 and2,321,023.

The control of pest organisms by the contacting thereof with one or moreof the new cyanopyridyl phosphorus compounds is illustrated by thefollowing examples.

i Example 4 Aqueous compositions, each containing one of the presentcyanopyridyl phosphorus compounds, are prepared as follows:

4 parts by weight of one of the cyanopyridyl phosphorus compounds, 0.08part of sorbitan trioleate (Span 85) and 0.02 part of a sorbitanmonolaurate polyoxyethylene derivative (Tween are dispersed in 40milliliters of acetone to produce a concentrate composition in the formof a Water-dispersible liquid. This concentrate composition is dispersedin water to provide aqueous compositions containing varying amounts ofthe cyanopyridyl phosphorus compound employed.

In this manner, aqueous compositions are separately prepared withO-(5-cyano-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(2-cyano-3-pyridyl) 0,0-diethyl phosphorothioate;

O-(6-cyano-3-pyridyl) O-isobutyl ethylphosphoramidate;

O-(3-cyano-2-pyridyl) O-n-butyl diethyl phosphoramidate;

O-(4-cyano-2-pyridyl) O-methyl di-n-butylphosphoramidothioate;

O-(S-cyano-Z-pyridyl) 0,0-dimethyl phosphate;

O- (6-cyano-2-pyridyl) O-n-propyl isobutylphosphoramidothioate;

O-(S-cyano- 2-pyridyl) 0,0-diethyl phosphate;

O-(5-cyano-2-pyridyl) 0,0-dimethyl phosphorothioate;

O-(5-cyano-2-pyridyl) O-isopropyl methylphosphoramidothioate;

O-(5-cyano-2-pyridyl) 0,0-di-n-propyl phosphorothioate;

O- Z-cyano-3 -pyridyl) O-ethylphosphoramidate;

O-(4-cyano-3-pyridyl) O,o-di-sec butylphosphate;

O-(5-cyano-3-pyridyl) 0,0-dimethy1 phosphorothioate;

0-(5-cyano-2-pyridyl) O-methyl methylphosphoramidothioate;

O-(6-cyano-3,5-dichloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-3-chloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-2-bromo-3 -pyridyl) O-isopropyl methylphosphoramidatc;

O-(3-cyano-5-chloro-4pyridyl) O-n-butyl O-methyl phosphorothioate; n 1

O-(3-cyano-5-bromo-2-pyridyl) 0,0-di-sec-butyl phosphate;

O-(5-cyano3-chloro-2-pyridyl) O-n-propyl sec-butylphosphoramidothioate;

O-(2-cyano-6-bromo-3-pyridyl) O-methyl phosphoramidate;

O-(5-cyano-3,6-dichloro-2-pyridyl) 0,0-diethyl phosphorothioate;O-(5-cyano-3,4,6-trichloro-2-pyridyl) 0,0-dimethyl phosphate;

k In further operations, aqueous compositions, each containing one ofthe present cyanopyridyl phosphorus compounds, are prepared as follows.

, A known quantity of one of the cyanopyridyl phosphorus compounds ismixed with a quantity of water, a quantity of an alkyl aryl sulfonate(Nacconol NR), and a quantity of a substituted benzoid alkyl sulphonicacid (Daxad 27), and the resulting mixture ballmilled together toproduce a composition containing 4000 parts by weight of thecyanopyridyl phosphorus compound employed, 300 parts by weight ofNacconol NR and 300 parts by weight of Daxad 27, per million parts ofultimate composition.

In this procedure, there are prepared aqueous compositions from each ofO-(S-cyano-Z-pyridyl) 0,0-diethyl phosphorothioate;

O-(2-cyano-3-pyridyl) 0,0-diethyl phosphorothioate;

O-(6-cyano-3-pyridyl) O-isobutyl ethylphosphoramidate;

O-(3-cyano-2-pyridyl) O-n-butyl diethyl-phosphoramidate;

O-(4-cyano-2-pyridyl) O-methyl di-n-butylphosphoramidothioate;

O-(5-cyano-2-pyridyl) 0,0-dimethyl phosphate;

O-(fi-cyano-Z-pyridyl) O-n-propyl isobutylphosphoramidothioate;

O-(5-cyano-2-pyridyl) 0,0-diethyl phosphate;

O-(S-cyano-Z-pyridyl) 0,0-dirnethyl phosphorothioate;

O-(S-cyano-Z-pyridyl) O-isopropyl methylphosphoramidothioate;

O-(S-cyano-Z-pyridyl) 0,0-di-n-propyl phosphorothioate;

O-(2-cyano-3-pyridyl) O-ethyl phosphoramidate;

O-(4-cyano-3-pyridyl) 0,0-di-sec-'hutyl phosphate;

O-(5-cyano-3-pyridyl) 0,0-dimethyl phosphorothioate;

O-(S-cyano-Z-pyridyl) O-methyl methylphosphoramidothioate;

O-(6-cyano-3,5-dichloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-3-chloro-2-pyridyl) 0,0-diethy1 phosphorothioate;

O-(S-cyano-Z-bromo-3-pyridyl) O-isopropyl methylphosphoramidate;

O-(3-cyanao-5-chloro-4-pyridyl) O-n-butyl O-methyl phosphorothioate;

O-(3-cyano-5-bromo-2-pyridyl) 0,0-di-sec-butyl phosphate;

O-(5-cyano-3-chloro-2-pyridyl) O-n-propyl sec-butylphosphoramidothioate;

O-(Z-cyano-6-bromo-3-pyridyl) O-methyl phosphoramidate;

O-(5-cyano-3,6-dichloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-3,4,6-trichloro-2-pyridyl) 0,0-dimethyl phosphate;

O-(5-cyano-2,4,6-tribromo-3-pyridyl) 0,0-dimethyl phosphorothioate; and

O-(5-cyano-3,6-dibromo-2-pyridyl) 0,0-diethyl phosphorothioate,

Compositions prepared according to these procedures of Example 5 can beemployed as treating compositions or can be diluted with additionalquantities of water to prepare aqueous treating compositions of lesserconcentrations.

Example 6 The cyanopyridyl phosphorus compounds of the present inventioncan also be employed to prepare aerosol compositions which areparticularly effective for localized control of pest organisms in andaround houses, barns, warehouses, and the like.

In representative operations, an aerosol formulation containing 1percent of one of the cyanopyridyl phosphorus compounds, 51 percent of apetroleum distillate, and 48 percent of dichlorodifiuoromethane isprepared by dispersing the cyanopyriclyl phosphorus compound in thepetroleum distillate and placing the resulting dispersion and liquiddichlorodifluoromethane within a closed cylinder provided with anorifice, opening of which is controlled by a valve operable from theexterior of the cylinder. In this manner, aerosol formulations areprepared with each of the following compounds:

O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphorothioate;

O-(2-cyano-3-pyridy1) 0,0-diethyl phosphorothioate;

O-(6-cyano-3-pyridyl) O-isobutyl ethylphosphoramidate;

O-(3-cyano-2-pyridyl) O-n-butyl diethylphosphoramidate;

O- (4-cyano-2-pyridyl) O-methyl di-n-butylphosphoramidothioate;

O-(S-cyano-Z-pyridyl) 0,0-dimethyl phosphate;

O-(6-cyano-2-pyridyl) O-n-propyl isobutylphosphoramidothioate;

O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphate;

O-(5-cyano-2-pyridyl) 0,0-dimethyl phosphorothioate;

O-(S-cyano-Z-pyridyl) O-isopropyl methylphosphoramidothioate;

O-(S-cyano-Z-pyridyl) 0,0-di-n-propyl phosphorothioate;

O-(2-cyano-3-pyridyl) O-ethyl phosphoramidate;

O-(4-cyano-3-pyridyl) 0,0-di-sec-butyl phosphate;

O-(5-cyano-3-pyridyl) 0,0-dimethyl phosphorothioate;

O-(5-cyano-2-pyridyl) O-methyl methylphosphorarnidothioate;

O-(6cyano-3,S-dichloro-Z-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-3-chloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-2-bromo-3-pyridyl) O-isopropyl methylphosphoramidate;

O-(3-cyano-5-chloro-4-pyridyl) O-n-butyl O-methyl phosphorothioate;

O-(3-cyano-5-bromo-2-pyridyl) 0,0-di-sec-butyl phosphate;

O-(5-cyano-3-chloro-2 pyridyl) O-n-propyl sec-butylphosphoramidothioate;

0-(2-cyano-6-brorno-3-pyridyl) O-methyl phosphoramidate;

O-(5-cyano-3,6-dichloro-2-pyridyl) 0,0-diethyl phosphorothioate;

O-(5-cyano-3,4,6-trichloro-2-pyridyl) 0,0-dimethyl phosphate;

O-(5-cyano-2,4,6-tribrorno-3-pyridyl) phorothioate; and

O-(5-cyano-3,6-dibromo-2-pyridyl) 0,0-diethyl phosphorothioate.

These compositions are particularly adapted to be employed as aerosolcompositions for the control of crawling insects, such as roaches,silverfisli, ants, spiders, and the like.

0,0-dimethyl phos- Example 7 An aqueous treating composition containingparts of O-(Z-cyano-B-pyridyl) 0,0-diethyl phosphorothioate per millionparts by weight of ultimate aqueous treating composition is preparedaccording to the procedures of Example 4. This aqueous treatingcomposition is employed for the control of Mexican bean beetles,(Epilaclma varivestis), in the third instar stage, on cranberry beanplants. The cranberry bean plants are wetted briefly with the aqueoustreating composition, the wetted plants permitted to dry, and the driedplants placed within a confined area and caused to be infested with aknown number of Mexican bean bettles. Thereafter, the infested plantsare held under good agricultural conditions for a period of severaldays. At the end of this period, the cranberry bean plants are examinedand it is found that there is obtained a complete kill of the Mexicanbean beetles.

13 Example 8 An aqueous treating composition containing 500 parts ofO-(2-cyano-3-pyridyl) 0,0-diethyl phosphorothioate per million parts byweight of ultimate aqueous treating composition is prepared according tothe procedures of Example4. A quantity of fruit and a known number ofplum-'curculio adults feeding thereon are wetted briefly with thisaqueous treating composition; thereafter, the treated fruit and curculioadults are permitted to dry and areheldfor .about'6 days underconditions conducive to the growth and well-being of plum curculioadults. At the end of the 6 day period, the fruit is examined todetermine'the percent mortality of plum curculio adults, and it-is foundthat there has been obtained a 100 percent kill and control of plumcurculio adults. 1

Example A 9 .Anaqueous treating composition containing 100 parts ofO-(S-cyano-Z-pyridyl) 0,0-dimethyl phosphorothioate per million parts byweight of ultimate aqueous treating composition -is prepared accordingto the procedures of Example 4. Houseflies (Musca domestica) areuniformly Wetted briefly with this aqueous treating composition andthereafter observed for mortality for 72 hours. It is found thattreatment of the housefiies in this manner with the subject compoundresults in a 100 percent kill of houseflies.

Example 10 Essentially the same results as in Example 9 are obtainedwhen O-(5-cyano-3-chloro-2-pyridyl) 0,0-diethyl phosphorothioate isemployed in the procedures of Example 9.

1 Example 11 O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphorothioate isdispersed in acetone and the resulting dispersion spread onto a groundpyrophyllite-aluminum silicate solid material to prepare a dustcomposition containing 2 percent of the subject compound. Thisdustcomposition is spread on the horizontal floor surface of an enclosedcockroach cage container to provide 2.0 milligrams of the subjectcompound per square foot of the surface. The sides of the container aregreased to prevent cockroaches from avoiding contact with the subjectcompound. Thereafter, a known number of American cockroaches(Periplaneta americana) are introduced into the container and thecontainer held in an environment conducive to the life processe of thecockroaches. Following the introduction of the cockroaches, thecontainer and the cockroaches placed therein are observed closely andcontinuously to determine the percent of early knock-down of thecockroaches. For the purposes of the evaluation, the inability tolocomote one full body length with coordination is considered toconstitute knock-down. It is found thatthere is a knock-down of 95percent of the cockroaches 36 minutes following the introduction of thecockroaches into the treated container.

Example 12 In procedures essentially the same as those employed inExample 11, except that there is utilized a dust composition containing0.5 percent of O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphorothioate, thesubject compound is evaluated for the percent mortality of Americancockroaches. This dust is spread on the floor surface to provide 0.5milligram of the compound per square foot of surface. In thisevaluation, following the introduction of the cockroaches into thetreated container, the container and cockroaches are held underconditions favorable to the growth and life processes of cockroaches,and periodic observations made, for 24 hours. At the end of the 24 hourperiod, there is found a complete kill and control of Americancockroaches.

14 Example 13 An aqueous compostion containing as sole active ingredientO-(S-cyano-Z-pyridyl) O-iso ropyl methylphosphoramidothioate is preparedaccording to the procedures of Example 4. The aqueous" treatingcomposition is applied to three fir plywood panels, evenly on bothsides, at the rate of 40 milligrams of the subject compound per squarefoot of surface area of the panels. Immediately thereafter, each of thethree panels is introduced into a separate screened cage; in the firstcagethere are placed a known number of housefiies (Musca domestica); inthe second cage there are placed a known number of American cockroaches(Periplaneta americana); and in the third cage, there are placed a knownnumber of German cockroaches (Blattella germanica'). Thereafter, thescreened cages are held under conditions favorable to the growth andwell-being of the insect organisms for a period of 24 hours. At the endof this period, the cages are examined and there is found a completekill and control of each of the subject organisms. 6 days later (a weekfollowing treatment of the plywood panels), new populations of knownnumbers of the three subject organisms are again placed, separately, onein each of the screened cages, to obtain a reinfestation, and the cagesexamined 24 hours later to determine the residual efiect of thetreatment upon the subject organisms. Subsequently, reinfestations aremade two weeks following treatment, 4 weeks following treatment, andevery 4 weeks thereafter for a period of time representing about 6months following treatment. 24 hours following each reinfestation, thescreened cages are examined and in each instance throughout the 6-monthperiod, there is found to be a complete kill and control of the subjectorganisms.

Example 14 An aerosol is prepared, according to the procedures ofExample 6, containing O-(S-cyano 2 pyridyl) 0,0-dimethyl phosphate assole active agent. This aerosol is employed for the control of a veryheavy infestation of silverfish (Lepisma saccharina) in the basement ofa house of natural stone, in which basement are stored books, clothing,and the like. The aerosol spray is directed at the basement walls andfloor and, in particular, into all crevices of the Walls and floor, sothat all sprayed surfaces are covered with a light but even deposit ofthe spray, representing about 10 milligrams per square foot. A period ofabout one day is permitted to pass and the basement then examined forthe presence of Silverfish. None are found. The spraying with theaerosol is repeated and the basement examined 24 hours after therepeated spraying. The area is closely examined a Week later and nosilverfish are found.

Example 15 An aerosol is prepared which contains O-(S-cyano-Z- pyridyl)0,0-dimethyl phosphorothioate as sole toxicant, according to theprocedures of Example 6 except that the propellant comprises percent ofthe total aerosol, the toxicant, 1 percent, and the petroleumdistillate, 19 percent. This aerosol is employed, in late May, as aspace spray for the control of spiders in a semi-enclosed laundrybuilding at a summer camp in the north temperature zone. Visible websare first mechanically removed, by handbrooms, and then the aerosol isdirected, in particular, at the upper portions of the room, the ceiling,dark lower portions, and the interior of a storage closet attachedthereto. After a week, the treated area is examined: substantial numbersof dead spiders found throughout, and no new webs or live spiders arefound.

Example 16 In other operations, a formulation prepared according to theprocedures of Example 5 and containing 50 parts of O (5 cyano 2 pyridyl)0,0-diethyl phosphate as sole active agent per million parts by weightof ultimate 15 formulation is employed for the control of fiddler crabs.

A coastal dike of earth, of which the thickness of a narrow section athigh tide level is variously from 1 to 3 feet, serving as a barrier toexclude incoming sea tides of brackish water, is infested with largenatural populations of fiddler crabs (not specifically identified butbelieved to be mostly Uca minax). The crabs burrows into the dikeconstitute a source of leakage of the brackish water beyond the dike andthreaten a general weakening of the dike structure.

The formulation is applied to the infested dike wall at low tide, in anamount sufficient to thoroughly drench. the dike surfaces. Shortly afterdeparture of the person making application, the crabs begin to emergefrom burrows into the dike; repeatedly, as individual fiddler crabsemerge, it is observed that each becomes inactivated. An examination ismade at low tide on the third day thereafter, and no fiddler crabs areseen.

Example 17 A composition is prepared according to the procedures ofExample and containing 500 parts of O (5 cyano- 2-pyridyl) O methylmethylphosphoramidothioate as sole toxicant per million parts by Weightof ultimate treating composition. Cranberry bean plants heavily infestedwith two-spotted spider mites in the egg and adult stages are wettedbriefly with this treating composition, the treated plants permitted todry, and the treated and dried plants held under favorable agriculturalconditions for a period of about 5 days. At the end of this period, theplants are examined to ascertain the percent kill and control oftwo-spotted spider mites in the adult stage, and to ascertain thepercent kill and control of two-spotted spider mites in the egg stage.It is found that there is a 100 percent kill of the two-spotted spidermites in the adult stage, and an essentially complete kill and controlof two-spotted spider mites in the egg stage.

Example 18 Essentially the same results as in Example 16 are obtainedwhen employing O (5 cyano 3 chloro 2- pyridyl) 0,0 diethylphosphorothioate as sole toxicant in the procedures of Example 16.

Example 19 An aerosol is prepared, according to the procedures ofExample 6, containing O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphorothioateas sole toxicant. This aerosol is employed for the control of a heavyinfestation of centipedes (Scolopendra morsitans) in a package-wrappingarea at the rear of a commercial Warehouse in the southeastern UnitedStates. Loose contents are removed, and the area superficially cleaned.During this clean-up, approximately 25 centipedes of lengths from 2 to 6inches are noticed. The said spray is directed at the walls of the areaand in and around facilities located in the area, so that all sprayedsurfaces are covered with a light but even deposit of the spray,representing about 25 milligrams of the compound per square foot. On thesecond day after this initial spraying, the spraying with the aerosol isrepeated. On the fifth day after the initial spraying, the area isclosely examined and no centipedes are found.

The O-loweralkyl phosphoramidochloridates andphosphoramidochloridothioates employed as starting materials inaccordance with the teachings of the present application are prepared byreacting two molecular proportions of a suitable amine with onemolecular proportion of an O-loweralkyl phosphorodichloridate orphosphorodichloridothioate at a temperature of from to 50 C. Uponcompletion of the reaction, the desired product is separated byconventional methods.

The 0,0-diloweralkyl phosphorochloridates and 0,0- diloweralkylphosphorochloridothioates, employed as starting materials as describedherein, are prepared in known procedures by reacting phosphorousoxychloride or phosphorus thiochloride with an alkyl metal alcoholate tointroduce two alkoxy groups into the molecule. Where it is desired toproduce the mixed diester, the phosphorus oxychloride or phosphorusthiochloride is successively reacted with different alcoholates. Goodresults are obtained when employing stoichiometric amounts of thereagents and operating at temperatures at which chloride of reaction isformed. Following the reaction, the desired products are separated byknown procedures.

The O-lower alkyl phosphorodichloridates or phosphorodichloridothioatesare prepared byv reacting a molecular excess of phosphoryl oxychlorideor phosphoryl thiochloride with a suitable loweraleohol. Good resultsare obtained when operating at temperatures of from 20 to C., andemploying from 4 to 10 moles of phosphoryl compound with one mole ofloweralcohol.

The alkali metal and tertiary amine salts of the cyanopyridinol, whichsalts are employed as starting materials for the compounds of thepresent invention, are prepared .in known procedures from thecorresponding cyanopyridinol compounds. The alkali metal salts areprepared by reacting the corresponding cyanopyridinol compounds with abase, which can be an alkali metal hydroxide or carbonate. The tertiaryamine salts are prepared by reacting together the correspondingcyanopyridinol compounds with the desired tertiary amine. Thesereactions to prepare the salts are preferably carried out in an inertliquid reaction medium.

The said alkali metal and tertiary amine salts are conveniently employedin situ; in such procedures, the desired salt, in the reaction medium inwhich prepared, is reacted with the phosphorochloridate orphosphorochloridothioate as hereinbefore taught. In other procedures,the cyanopyridyl phosphorus compounds of the present invention areprepared by reacting together the cyanopyridinol compound, the base ortertiary amine, and the phosphorochloridate or phosphorochloridothioate;in these procedures, the same reaction conditions taught hereinabove forthe reaction of the said alkali metal or tertiary amine salt withphosphorochloridate or phosphorochloridothiate are employed.

The cyanopyridinol compounds are also prepared in known procedures; inthese procedures, a cyano moiety is introduced onto the nucleus of apyridinol compound. See pp. 230-232 of Pyridine and Derivatives, partthree, edited by Klingsber-g (Interscience Publishers, New York, 1962).In preparing cyanopyridinol compounds, good results are generallyobtained when employing the procedure wherein a nuclear halogen atom ona halopyridinol is replaced, or one of a plurality of nuclear halogenatoms on a polyhalopyridinol is selectively replaced, with a cyanogroup. The halopyridinols are prepared by the known processes ofhydrolysis and halogenation as set forth at Rec. Trav. Chem., at 69,684-699 and 1281-1288 (1950); and 74, 59 (1955); and at J. Chem. Soc.83,400. See'also Pyridine and Its Derivatives, op. cit., pp. 571- 582.In an alternative method, a cyanopyridinol wherein n=0 is preparedaccording to the known procedures for introduction of a cyano moietyonto the nucleus of a pyridinol compound, and the said cyanopyridinol isthereafter halogenated. This halogenation is accomplished by the knownhalogenation processes referred to above for the halogenation ofpyridinols to prepare halopyridinols.

I claim:

1. Compound of the formula wherein Z represents a member selected fromthe group consisting of oxygen and sulfur; X represents a memberselected from the group consisting of bromo and chloro; R representsloweralkoxy; R represents a member selected from the group consisting ofloweralkoxy, amino, and References Cited igvsgerattjliygaiglcilngivind nrepresents an integer of from 0 UNITED STATES PATENTS 2.O-(5-cyano-2-pyridyl) 0,0-diethy1phosphorothioate. 2,881,201 5/1959Schmdel' 260461 3. O-(S-cyano-Z-pyridyl) 0,0-dimethyl phosphate. 5 4O-(2-cyano-3-pyridyl) 0,0-diethylphosphorothioate. FOREIGN PATENTSO-(S-cyano-Z-pyridyl) 0,0-dimethyl phosphorothio- 3,813,079 7/1963Japan- 6 O-(S-cyano-Z-pyridyl) 0,0-diethyl phosphate. OTHER REFERENCES7- O (6 cyano 3 pyridy1) o isobutyl ethylphosphorami Derwent JapanesePatents Report, vol. 2, No. 29

date. 10 (1963) pp. 7-8, General Organic 13,079/63 For. Pat. Jrl. r01ZSHiOOz; t(e5.- :yano-3-ch10ro-2-pyr1dyl) O,O-d1ethyl ph p OHN D. RADOLPH, Primary Examiner.

9. O-(2-cyano-4-pyridyl) O-ethyl O-methyl phosphate. A. L. ROTMAN,Assistant Examiner.

